Dithiocarbamylacetoneoxime carbamate acaricides and insecticides

ABSTRACT

DITHIOCARBAMYLACETONEOXIME CARBAMATES HAVING THE GENERAL FORMULA   IN WHICH R AND R1 ARE INDEPENDENTLY METHYL OR ETHYL, AND R2 IS LOWER ALKYL, PREFERABLY METHYL. THE COMPOUNDS ARE USEFUL AS ACARICIDES AND INSECTICIDES .   R1-N(-R)-C(=S)-S-CH2-C(-CH3)=N-OOC-NH-R2

United States Patent 3,743,743 DITHIOCARBAMYLACETONEOXIME CARBA- MATEACARICIDES AND INSECTICIDES Arnold D. Gutman, Berkeley, Calif., assignorto Stauffer Chemical Company, New York, N.Y.

No Drawing. Original application Mar. 18, 1969, Ser. No. 808,342, nowPatent No. 3,642,856. Divided and this application Sept. 3, 1971, Ser.No. 177,811

Int. Cl. A01n 9/12 U.S. Cl. 424-300 3 Claims ABSTRACT OF THE DISCLOSUREDithiocarbamylacetoneoxime carbamates having the general formula s o\NHISCHZC=NO(UJNHRI R1 3 in which R and R are independently methyl orethyl, and R is lower alkyl, preferably methyl. The compounds are usefulas acaricides and insecticides.

This is a division of application Ser. No. 808,342, filed Mar. 18, 1969.

This invention relates to certain novel compounds and their utility asacaricides and insecticides. The compounds aredithiocarbamylacetoneoxime carbamates. The compounds are of particularinterest because they are nonphosphorus-containing compounds which haveacaricidal and insecticidal properties. More specifically, thisinvention relates to compounds of the formula 5 o NiisCH,c=N0iiNHR,

R1 CH: wherein R and R are independently methyl or ethyl and R is loweralkyl having from 1 to about 4 carbon atoms inclusive, preferablymethyl. Also included is a method of preparing, using and applying saidcompositions.

The compounds of this invention can be prepared by one of severaldifferent methods depending upon the nature of the starting materials.One such method employed in preparing the compounds is the condensationof an appropriately substituted dithiocarbamylacetone and hydroxylaminehydrochloride to prepare the intermediate dithiocarbamylacetoneoxime.This material is then reacted with a lower alkyl isocyanate, such asmethyl isocyanate, to prepare a dithiocarbamylacetoneoximino- N-loweralkyl carbamate such as dithiocarbamylacetoneoxime-N-methyl carbamate.This reaction proceeds readily in the liquid phase. The employment of aninert organic solvent is also useful, facilitating processing as well asagitation of the reactants.

It has been found that the compounds of the present invention areparticularly effective as acaricides and insecticides.

The preparation of compounds of the present inven-- tion is moreparticularly illustrated by the following examples:

EXAMPLE I Preparation of N,N-dimethyldithiocarbamylacetoneoximeintermediate In a 500 ml. three-neck flask fitted with a thermometer,stirrer and dropping funnel, 17.7 gm. (0.1 mole) of N,N-dimethyldithiocarbamylacetone and 7.6 gm. (0.11 mole) of hydroxylaminehydrochloride are combined in a solution of 30 ml. ethanol in 300 ml. ofwater. The mixture is rapidly stirred and a solution of 7.5 gm. (0.06

3,743,743 Patented July 3, 1973 mole) sodium carbonate monohydrate in 25ml. of water is added over a period of 15 minutes. After the addition iscomplete, the mixture is stirred at room temperature for two hours. Thereaction mixture is then poured into 300 ml. of water. The aqueousmixture is extracted with 3-100 ml. portions of CHCl The CHCl solutionis dried with anhydrous magnesium sulfate and evaporated under reducedpressure. There is obtained 15.8 gm. (82.5% of theory) ofN,N-dimethyldithiocarbamylacetoneoxime, a low melting solid.

EXAMPLE H Preparation ofN,N-dimethyldithiocarbamylacetoneoximino-N-methyl carbamate EXAMPLE IIIPreparation of N,N-diethyldithiocarbamylacetoneoximino-N-methylcarbamate In a similar manner as Example II, employing 9 gm. (0.041mole) of N,N-diethyldithiocarbamylacetoneoxime, there is obtained 10 gm.(88% of theory), of N,N-diethyldithiocarbamylacetoneoximino-N'-methylcarbamate, N =1.5700.

As previously mentioned, the herein described compositions produced inthe above-described manner are biologically active compounds which areuseful and valuable in controlling acarids. The compounds of thisinvention are tested in the following manner: Compound numbers,hereinafter mentioned, correspond to the example numbers in which thepreparation of the compound is described, supra.

Acaricidal evaluation test: Two-spotted mite, Tetranychus telarius(Linm) is employed in tests for miticides. Young pinto bean plants inthe primary leaf stage are used as the host plants. The young pinto beanplants are infested with several hundred mites. Dispersions of candidatematerials are prepared by dissolving 0.1 gram in 10 ml. of a suitablesolvent, usually acetone. Aliquots of the toxicant solutions aresuspended in water containing 0.0175% v./v. Sponto 221 (polyoxy-ethyleneether of alkylated phenols blended with organic sulfonates), anemulsifying agent, the amount of water being sufiicient to giveconcentrations of active ingredient ranging from 0.05% to 0.0008%. Thetest suspensions are then sprayed on the infested pinto bean plants.After seven days, mortalities of post-embryonic and ovicidal forms weredetermined. The percentage of kill is determined by comparision withcontrol plants which are infested but not sprayed with the candidatecompounds. The LD value is calculated using well-known procedures. Thecompound of Example H has an LD of 0.03% against the postembryonic formof the mite species and 0.03% against the mite eggs.

Aphid evaluation test: The compounds are also active against bean aphid(Aphis fabae (Scop.)) as a contact toxicant. The same test procedure andsolution formulation as given for the two-spotted mite test above isused for the aphid test. Nasturtium (Tropaeolum sp.) plantsapproximately two to three inches tall are used as the host plant.Several hundred aphids are used to infest the plants. The treated plantsare held for two days before mortalities of the aphids is determined.The percentage kill is determined by comparison with untreated infestedplants. The LD value is calculated. The compound of Example II has an LDagainst bean aphid of 0.01% and the compound of example number III hasan LD value against bean aphid of 0.03%.

The concentration of a compound of the present invention constituting aneffective amount of the best mode of administration to an insect oracarid pest or its habitat may be easily determined by those skilled inthe art of pest control, as exemplified by the procedures describedhereinabove. In practice, the compounds are formulated with an inertcarrier utilizing methods well-known to those skilled in the art,thereby making them suitable for application as dusts, sprays, trenchesand the like. Organic solvents, such as aliphatic and alicyclic ketones,hydrocarbons such as benzene, xylenes, toluene, petrols, furthermore,chlorinated and fluorinated hydrocarbons such as chlorobenzenes, areparticularly suitable for preparation of solutions. The activesubstances according to the invention may also be applied in aqueouspreparations, such as, for example, dispersions (emulsions andsuspensions). For the preparation of an emulsion, the substances arehomogenized in water in one of the above-mentioned solvents, preferablyin the presence of a dispersing agent. Cationic, anionic and nonionicpreparations my be mentioned as dispersing agents or emulsifiers, forexample, quaternary ammonium compounds, soaps, alkali and earth alkalinesalts of long-chain aliphatic sulfuric acid monoesters, andpoly-ethylene glycol ethers of fatty alcohols or alkyl phenols.Film-forming and adhesion agents may furthermore be added to theemulsions or dispersions. For dusts and scattering agents, the activesubstances are added in various ways to finely ground or granulatedcarriers which may be inert, acid or alkaline. The carriers may beimpregnated with the solutions of the active substances as describedabove. Inorganic substances, such as silicates, bentonites, zeolites,kieselguhr,

diatomaceous earth, glass powder, talc, boric acid, tricalcium phosphateand in some cases calcium carbonate, for example, in the form ofprepared chalk, quick-lime and finely-ground lime may be regarded ascarriers for these forms of preparation. Organic substances such as woodmeal, cork dust, walnut shell powder, or granules may serve as carriers.To insure contact with the pests, the active substances can be used withlures and baits. The biological effect may likewise be extended byadding substances containing bactericidal, fungicidal, nematocidal ortheir insecticidal properties.

What is claimed is:

1. A method for controlling insects and acarids which comprises applyingto said insects and acarids an insecticidally or acaricidally eifectiveamount of a compound having the formula in which R and R areindependently methyl or ethyl and R is lower alkyl having from 1 toabout 4 carbon atoms, inclusive.

2. The method of claim 1 in which R, R and R are each methyl.

3. The method of claim 1 in which R and R are both ethyl and R ismethyl.

References Cited UNITED STATES PATENTS 3,078,306 2/1963 Von Schickh eta1. 260566 3,211,770 10/1965 Pyne 424-300 3,277,142 10/1966 Zerbe et al.424300 3,299,137 1/1967 Payne Jr. et al 260566 3,400,153 9/1968 PayneJr. et a1 260566 3,418,362 12/1968 Adonwardene et a1. 424-300 ALBERT T.MEYERS, Primary Examiner L. SCHENKMAN, Assistant Examiner

